WO2022145318A1 - アルカリ金属イオン伝導性固体電解質およびその製造方法、非水電解質二次電池用セパレータおよびその製造方法、ならびに非水電解質二次電池 - Google Patents

アルカリ金属イオン伝導性固体電解質およびその製造方法、非水電解質二次電池用セパレータおよびその製造方法、ならびに非水電解質二次電池 Download PDF

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WO2022145318A1
WO2022145318A1 PCT/JP2021/047655 JP2021047655W WO2022145318A1 WO 2022145318 A1 WO2022145318 A1 WO 2022145318A1 JP 2021047655 W JP2021047655 W JP 2021047655W WO 2022145318 A1 WO2022145318 A1 WO 2022145318A1
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alkali metal
metal ion
negative electrode
solid electrolyte
conductive solid
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PCT/JP2021/047655
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English (en)
French (fr)
Japanese (ja)
Inventor
恒平 原
基浩 坂田
拡哲 鈴木
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2022573029A priority Critical patent/JPWO2022145318A1/ja
Priority to EP21915178.4A priority patent/EP4270525A4/en
Priority to US18/269,392 priority patent/US20240322232A1/en
Priority to CN202180087749.2A priority patent/CN116711089B/zh
Publication of WO2022145318A1 publication Critical patent/WO2022145318A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention mainly relates to an alkali metal ion conductive solid electrolyte for use as a material for a non-aqueous electrolyte secondary battery.
  • an organic electrolytic solution is permeated or immersed in a group of electrodes wound or laminated via a liquid holder serving as a separator between a positive electrode plate and a negative electrode plate, and lithium ions are repeatedly stored and released.
  • a liquid holder for a lithium secondary battery used for a secondary battery the liquid holder has a multilayer structure having at least two hydrophilic fiber layers having different porosity, and is on the interface side with the negative electrode plate.
  • the pore ratio of the fiber layer is smaller than the pore ratio of the fiber layer on the interface side with the positive electrode plate, and the average pore ratio of the entire fiber layer is 50% or more.
  • Patent Document 2 proposes a solid polymer electrolyte membrane which is a membrane made of sulfoalkyl cellulose obtained by sulfoalkylating cellulose and is characterized in that the membrane is crosslinked by a cross-linking agent. Further, Patent Document 2 proposes to use the solid polymer electrolyte membrane in a fuel cell.
  • the liquid holder for a lithium secondary battery of Patent Document 1 is composed of a fiber layer, it cannot restrict the movement of substances other than lithium ions between the positive electrode and the negative electrode.
  • the solid polyelectrolyte membrane of Patent Document 2 has proton conductivity, but does not have lithium ion conductivity, and is not applicable to a non-aqueous electrolyte secondary battery.
  • One aspect of the present invention relates to an alkali metal ion conductive solid electrolyte containing an organic polymer having an alkali metal sulfonate group.
  • Another aspect of the present invention relates to a separator for a non-aqueous electrolyte secondary battery containing the alkali metal ion conductive solid electrolyte.
  • Yet another aspect of the present invention is the positive electrode, the negative electrode, the separator for a non-aqueous electrolyte secondary battery interposed between the positive electrode and the negative electrode, the first electrolytic solution in contact with the positive electrode, and the negative electrode.
  • the present invention relates to a non-aqueous electrolyte secondary battery comprising a second electrolytic solution to be contacted and having different compositions of the first electrolytic solution and the second electrolytic solution.
  • Yet another aspect of the present invention comprises a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolytic solution in contact with the positive electrode and the negative electrode, and at least the positive electrode and the negative electrode.
  • a non-aqueous electrolyte secondary battery provided with the alkali metal ion conductive solid electrolyte.
  • an alkyl halide sulfonate is added to an alkaline solution containing a raw material organic polymer having a plurality of hydroxyl groups to form a hydrogen atom of at least one of the hydroxyl groups in the formula: -R-SO 3 X (.
  • the present invention relates to a method for producing an alkali metal ion conductive solid electrolyte, which comprises a step of substituting an alkyl sulfonate group represented by (where R is an alkylene group and X is an alkali metal atom).
  • Yet another aspect of the present invention relates to a method for manufacturing a separator for a non-aqueous electrolyte secondary battery, which comprises a step of forming the alkali metal ion conductive solid electrolyte into a sheet.
  • alkali metal ion conductive solid electrolyte According to the alkali metal ion conductive solid electrolyte according to the present invention, it is possible to secure alkali metal ion conduction between the positive electrode and the negative electrode while separating the positive electrode and the negative electrode.
  • the novel features of the invention are described in the appended claims, but the invention is further described in detail with respect to both configuration and content, in conjunction with other objects and features of the invention, with reference to the drawings below. It will be well understood.
  • the alkali metal ion conductive solid electrolyte contains an organic polymer (hereinafter referred to as LSP) having an alkali metal sulfonate group (for example, a lithium sulfonate group).
  • LSP organic polymer
  • LSP can be used, for example, by introducing an alkali metal sulfonate group into a raw material organic polymer, or by introducing a sulfo group (-SO 3 H) and then substituting the hydrogen atom with an alkali metal such as Li, Na, or K. It can be easily synthesized.
  • the alkali metal sulfonate group (-SO 3 X: X is an alkali metal atom) is responsible for hopping of alkali metal ions and imparts alkali metal ion conductivity to the organic polymer.
  • the raw material organic polymer it suffices if a sulfonate group or a sulfo group can be introduced.
  • the raw material organic polymer may have a plurality of hydroxyl groups.
  • the hydroxyl group can be substituted with a sulfo group or a sulfonate group or a substituent having these by various methods.
  • the mass (EW value) of the organic polymer per mol of the alkali metal sulfonate group may be 168 g / mol or more and 300 g / mol or less.
  • a raw material organic polymer having as many hydroxyl groups as possible may be used.
  • Polysaccharides may be used as the raw material organic polymer.
  • LSP synthesized from polysaccharides is a derivative of polysaccharides.
  • Polysaccharide is a general term for polymers having a structure in which a plurality of monosaccharide molecules are bonded via glycosidic bonds.
  • Examples of the basic structures of polysaccharides that can be used include aldoses, kets, pyranose and furanose.
  • Examples of the monosaccharide molecule (monomer) constituting the polysaccharide include triose, tetrose, pentose, hexose, and heptose. Of these, aldopentose, ketopentose, aldohexose, and ketohexose are desirable.
  • polysaccharides include, for example, cellulose, hemicellulose, pectin, alginic acid, pullulan, mannan, xanthan gum, guagam, starch, glycogen, chitin, dextran, agarose, carrageenan, heparin, hyaluronic acid, glucomannan or derivatives thereof ( Salts, esterifieds, etherifieds, amidates, etc.) and the like.
  • cellulose has excellent heat resistance, abundant resources, and can be obtained at low cost.
  • the LSP may further have a plurality of hydroxyl groups.
  • the hydrogen atom of the hydroxyl group can be replaced with an alkali metal atom. This makes it possible to further enhance the alkali metal ion conductivity of the LSP.
  • the alkali metal sulfonate group may be a part of an alkali metal alkyl sulfonate group represented by the formula: —R—SO 3 X (R is an alkylene group and X is an alkali metal atom).
  • the alkylene group R may be, for example, an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms.
  • the alkylene group R may be, for example, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, or an n-hexylene group.
  • the LSP may be formed into a sheet to produce a separator for a non-aqueous electrolyte secondary battery.
  • a separator a microporous membrane, papermaking, non-woven fabric and the like are generally used.
  • a dense film is required to separate the positive electrode and the negative electrode.
  • the dense film containing LSP can be used as a separator that allows alkali metal ion conduction between the positive electrode and the negative electrode while separating the positive electrode and the negative electrode.
  • a dense film containing LSP can be obtained.
  • LSPs with alkali metal sulfonate groups are water soluble.
  • the aqueous solution containing LSP can be formed into a dense film by various methods.
  • a dense film can be obtained by applying an aqueous solution containing LSP to a flat surface of a base sheet and volatilizing water from the coating film.
  • the separator may be non-perforated.
  • Non-pore means that unlike a general separator, there are no pores or gaps that allow the movement of the electrolytic solution.
  • non-perforated means substantially non-perforated, and the presence of unavoidably formed pinholes and the like is permissible.
  • the non-perforated separator has a very high air permeability.
  • the air permeability (air permeation resistance) of the separator may be, for example, 10,000 seconds / 100 mL or more.
  • the air permeability is measured by, for example, a B-type tester (Garley type densometer) in accordance with the section of "21.2 Air permeability B method (Garley test method)" (JIS P 8117) specified in JIS C2300. be able to.
  • the dense film containing LSP may be, for example, a film containing 70% by mass or more of LSP, a film containing LSP having a content of 95% by mass or more, and 100% of LSP. May be.
  • the thickness of the dense film containing LSP may be, for example, 0.001 ⁇ m or more and 100 ⁇ m or less, 0.01 ⁇ m or more and 90 ⁇ m or less, and 0.1 ⁇ m or more and 80 ⁇ m or less. It may be 1 ⁇ m or more and 70 ⁇ m or less.
  • a dense film containing an organic polymer having a lithium sulfonate group is, for example, 1.0 ⁇ 10 -4 S / cm or more, and further 1.0 ⁇ 10 -3 S / cm or more at 25 ° C. ( Alternatively, it indicates an ionic conductivity (for example, lithium ion conductivity) of 2.0 ⁇ 10 -3 S / cm or more.
  • the ionic conductivity of the film is 10-8 S / cm or less.
  • a raw material organic polymer for example, a polysaccharide
  • an organic solvent an alkali may be dissolved, and for example, a protonic solvent such as alcohol, an ether, an ester, or the like can be used.
  • a protonic solvent such as alcohol, an ether, an ester, or the like.
  • the alkali NaOH, KOH, LiOH and the like can be used, but the alkali is not particularly limited.
  • a halogenated alkyl sulfonate is added to the reaction solution being stirred, and the hydrogen atom of at least one hydroxyl group of the raw material organic polymer is represented by the formula: —R—SO 3 X (R is an alkylene group and X is an alkali metal atom). ) Substitute with the alkylsulfonate group.
  • a halogenated alkyl sulfonate for example, a bromoalkyl sulfonate can be used. Specifically, sodium 2-bromoethanesulfonate, potassium 2-bromoethanesulfonate, lithium 2-bromoethanesulfonate and the like can be used.
  • the reaction solution may be heated to promote the substitution reaction.
  • the temperature of the reaction solution may be, for example, 50 ° C to 80 ° C.
  • the reaction time is not particularly limited, but the reaction may be sufficiently proceeded over, for example, 10 hours or more (preferably 50 to 100 hours).
  • the alkali metal atom X When the alkali metal atom X is other than Li (Na, K, etc.), the alkali metal atom X may be ion-exchanged with Li.
  • the organic polymer into which the alkylsulfonate group has been introduced is water soluble.
  • a water-soluble polymer When a water-soluble polymer is dissolved in water to prepare an aqueous solution and the aqueous solution is brought into contact with a strongly acidic ion-exchange resin, the alkali metal atom is replaced with a hydrogen atom to obtain an organic polymer having a sulfoalkyl group.
  • LiOH lithium hydroxide
  • the non-aqueous electrolyte secondary battery according to the present embodiment includes a positive electrode, a negative electrode, a separator containing an LSP interposed between the positive electrode and the negative electrode, and an electrolytic solution in contact with the positive electrode and the negative electrode.
  • a separator containing an LSP By using a separator containing an LSP, the transfer of eluates or by-products from one of the positive and negative electrodes to the other is restricted and side reactions are suppressed. Therefore, it is possible to improve the durability, output characteristics, and the like of the battery.
  • the separator containing LSP may be used in combination with a general microporous membrane, papermaking, non-woven fabric or the like (hereinafter, also referred to as a conventional separator).
  • a separator containing LSP and a conventional separator may be used in combination.
  • a composite separator of the conventional separator and the LSP may be formed and used by applying an aqueous solution containing LSP to one or both surfaces of the conventional separator and volatilizing water from the coating film.
  • An example of the structure of a non-aqueous electrolyte secondary battery is a structure in which an electrode group in which a positive electrode and a negative electrode are wound via a separator is housed in an exterior body together with an electrolytic solution.
  • the present invention is not limited to this, and other forms of electrodes may be applied.
  • a laminated electrode group in which a positive electrode and a negative electrode are laminated via a separator may be used.
  • the form of the non-aqueous electrolyte secondary battery is not limited, and may be, for example, a cylindrical type, a square type, a coin type, a button type, a laminated type, or the like.
  • the non-aqueous electrolyte secondary battery according to the present embodiment has a positive electrode, a negative electrode, a separator containing an LSP interposed between the positive electrode and the negative electrode, a first electrolytic solution in contact with the positive electrode, and a second electrolytic solution in contact with the negative electrode. It is equipped with an electrolytic solution.
  • the composition of the first electrolytic solution and the second electrolytic solution are different.
  • the first electrolytic solution has a composition suitable for the positive electrode side
  • the second electrolytic solution has a composition suitable for the negative electrode side.
  • the first electrolytic solution has a composition excellent in oxidation resistance
  • the second electrolytic solution has a composition excellent in reduction resistance.
  • the positive electrode is impregnated with the first electrolytic solution
  • the negative electrode is impregnated with the second electrolytic solution
  • the positive electrode and the negative electrode are separated via a separator containing an LSP.
  • the electrode group may be formed by winding.
  • the space in which the positive electrode is accommodated and the space in which the negative electrode is accommodated may be separated.
  • Examples of such a structure include an inside-out structure.
  • a battery having an inside-out structure has a tubular positive electrode and a tubular negative electrode. The other is inserted in one of the tubular positive electrode and the tubular negative electrode.
  • the inside-out structure includes, but is not limited to, an alkaline dry cell type and a Kenzan type.
  • the non-aqueous electrolyte secondary battery according to the present embodiment includes a positive electrode, a negative electrode, a separator containing an LSP interposed between the positive electrode and the negative electrode, and an electrolytic solution in contact with the positive electrode and the negative electrode, and the positive electrode and the negative electrode are provided. At least one is equipped with an LSP.
  • LSP may be contained in at least one of the positive electrode mixture provided in the positive electrode and the negative electrode mixture provided in the negative electrode. Further, at least a part of the surface of the particles of the positive electrode active material contained in the positive electrode mixture may be coated with LSP in advance, or at least a part of the surface of the negative electrode active material contained in the negative electrode mixture in advance may be covered with LSP. It may be covered with. Further, an LSP coating film may be formed on the surface of the positive electrode, or an LSP coating film may be formed on the surface of the negative electrode. This suppresses side reactions at the positive and negative electrodes.
  • the battery includes a bottomed square battery case 4, an electrode group 1 housed in the battery case 4, and a non-aqueous electrolyte (not shown).
  • the electrode group 1 has a long strip-shaped negative electrode, a long strip-shaped positive electrode, and a separator interposed between them.
  • the negative electrode current collector of the negative electrode is electrically connected to the negative electrode terminal 6 provided on the sealing plate 5 via the negative electrode lead 3.
  • the negative electrode terminal 6 is insulated from the sealing plate 5 by a resin gasket 7.
  • the positive electrode current collector of the positive electrode is electrically connected to the back surface of the sealing plate 5 via the positive electrode lead 2. That is, the positive electrode is electrically connected to the battery case 4 that also serves as the positive electrode terminal.
  • the peripheral edge of the sealing plate 5 is fitted to the open end portion of the battery case 4, and the fitting portion is laser welded.
  • the sealing plate 5 has an injection hole for a non-aqueous electrolyte, and is closed by the sealing 8 after injection.
  • the negative electrode may have a negative electrode current collector.
  • the movement of electrons in the negative electrode during charging and discharging is mainly due to the precipitation and dissolution of the lithium metal in the negative electrode.
  • 70 to 100% (for example, 80 to 100% or 90 to 100%) of electron transfer (current in another aspect) in the negative electrode during charging and discharging is due to the precipitation and dissolution of the lithium metal.
  • the negative electrode may include a negative electrode current collector and a negative electrode mixture layer supported on the surface of the negative electrode current collector.
  • the negative electrode mixture layer can be formed by applying a negative electrode slurry in which a negative electrode mixture is dispersed in a dispersion medium to the surface of a negative electrode current collector and drying it. The dried coating film may be rolled if necessary.
  • the negative electrode mixture layer may be formed on one surface of the negative electrode current collector, or may be formed on both surfaces.
  • the negative electrode mixture contains a negative electrode active material as an essential component, and can include a binder, a conductive agent, a thickener and the like as optional components.
  • a negative electrode active material the above-mentioned negative electrode material (composite particles having a conductive layer) is used.
  • the negative electrode active material a material having a graphite-type crystal structure capable of reversibly storing and releasing lithium ions, for example, natural graphite or artificial graphite, non-graphitizable carbon (hard carbon), easily graphitizable carbon (soft). Examples thereof include carbon materials such as carbon), Si-containing materials, and Sn-containing materials.
  • the negative electrode may contain one kind of negative electrode active material, or may contain two or more kinds in combination. Of the negative electrode active materials, carbonaceous materials and Si-containing materials are preferable. A carbonaceous material and a Si-containing material may be combined.
  • the negative electrode current collector a non-perforated conductive substrate (metal foil, etc.) and a porous conductive substrate (mesh body, net body, punching sheet, etc.) are used.
  • the material of the negative electrode current collector include stainless steel, nickel, nickel alloy, copper, and copper alloy.
  • the thickness of the negative electrode current collector is not particularly limited, but is preferably 1 to 50 ⁇ m, more preferably 5 to 20 ⁇ m, from the viewpoint of the balance between the strength and weight reduction of the negative electrode.
  • the negative electrode active material for example, a known material capable of occluding and releasing lithium ions is used.
  • the negative electrode active material include elemental lithium metal, lithium alloy, silicon, silicon alloy, graphite, non-graphitizable carbon, lithium-containing metal oxide and the like.
  • the binder may be a resin material, for example, a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride (PVDF); a polyolefin resin such as polyethylene or polypropylene; a polyamide resin such as an aramid resin; a polyimide resin such as polyimide or polyamideimide.
  • PVDF polytetrafluoroethylene or polyvinylidene fluoride
  • a polyolefin resin such as polyethylene or polypropylene
  • a polyamide resin such as an aramid resin
  • a polyimide resin such as polyimide or polyamideimide.
  • Acrylic resin such as polyacrylic acid, methyl polyacrylic acid, ethylene-acrylic acid copolymer; vinyl resin such as polyacrylonitrile and vinyl acetate; polyvinylpyrrolidone; polyether sulfone; styrene-butadiene copolymer rubber (SBR)
  • SBR s
  • the conductive agent examples include carbons such as acetylene black; conductive fibers such as carbon fibers and metal fibers; carbon fluoride; metal powders such as aluminum; conductive whiskers such as zinc oxide and potassium titanate; Examples thereof include conductive metal oxides such as titanium oxide; and organic conductive materials such as phenylene derivatives.
  • the conductive agent one type may be used alone, or two or more types may be used in combination.
  • the thickener examples include carboxymethyl cellulose (CMC) and its modified product (including salts such as Na salt), cellulose derivatives such as methyl cellulose (cellulose ether and the like); and Ken, a polymer having a vinyl acetate unit such as polyvinyl alcohol.
  • CMC carboxymethyl cellulose
  • cellulose ether and the like examples include cellulose derivatives such as methyl cellulose (cellulose ether and the like); and Ken, a polymer having a vinyl acetate unit such as polyvinyl alcohol.
  • the thickener may be used alone or in combination of two or more.
  • the dispersion medium is not particularly limited, and examples thereof include water, alcohols such as ethanol, ethers such as tetrahydrofuran, amides such as dimethylformamide, N-methyl-2-pyrrolidone (NMP), and a mixed solvent thereof. ..
  • the positive electrode may include a positive electrode current collector and a positive electrode mixture layer supported on the surface of the positive electrode current collector.
  • the positive electrode mixture layer can be formed by applying a positive electrode slurry in which a positive electrode mixture is dispersed in a dispersion medium to the surface of a positive electrode current collector and drying it. The dried coating film may be rolled if necessary.
  • the positive electrode mixture layer may be formed on one surface of the positive electrode current collector, or may be formed on both surfaces.
  • the positive electrode mixture contains a positive electrode active material as an essential component, and may contain a binder, a conductive agent, and the like as optional components.
  • As the dispersion medium of the positive electrode slurry NMP or the like is used.
  • a lithium-containing composite oxide can be used as the positive electrode active material.
  • a lithium-containing composite oxide can be used as the positive electrode active material.
  • Me is Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, It is at least one selected from the group consisting of Al, Cr, Pb, Sb, and B).
  • a 0 to 1.2
  • b 0 to 0.9
  • c 2.0 to 2.3.
  • the a value indicating the molar ratio of lithium increases or decreases depending on charging and discharging.
  • Li a Ni b Me 1-b O 2 (Me is at least one selected from the group consisting of Mn, Co and Al, 0 ⁇ a ⁇ 1.2, 0.3 ⁇ b ⁇ ".
  • the binder and the conductive agent the same ones as those exemplified for the negative electrode can be used.
  • the conductive agent graphite such as natural graphite or artificial graphite may be used.
  • the shape and thickness of the positive electrode current collector can be selected from the shape and range according to the negative electrode current collector.
  • Examples of the material of the positive electrode current collector include stainless steel, aluminum, aluminum alloy, and titanium.
  • the electrolytic solution contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • the concentration of the lithium salt in the electrolytic solution is preferably, for example, 0.5 mol / L or more and 2 mol / L or less. By setting the lithium salt concentration in the above range, an electrolytic solution having excellent ionic conductivity and appropriate viscosity can be obtained.
  • the lithium salt concentration is not limited to the above.
  • cyclic carbonate ester for example, cyclic carbonate ester, chain carbonate ester, cyclic carboxylic acid ester, chain carboxylic acid ester and the like are used.
  • cyclic carbonic acid ester examples include propylene carbonate (PC) and ethylene carbonate (EC).
  • chain carbonate ester examples include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • chain carboxylic acid ester examples include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate and the like.
  • the non-aqueous solvent one type may be used alone, or two or more types may be used in combination.
  • lithium salt examples include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiB 10 Cl 10 , LiB 10 Cl 10, and LiCl. , LiBr, LiI, borates, imide salts and the like.
  • borates include bisoxalate lithium borate, difluorooxalate lithium borate bis (1,2-benzenegeolate (2-) -O, O') lithium borate, and bis (2,3-naphthalenedio).
  • Imide salts include bisfluorosulfonylimide lithium (LiN (FSO 2 ) 2 ), bistrifluoromethanesulfonate imide lithium (LiN (CF 3 SO 2 ) 2 ), and trifluoromethanesulfonate nonafluorobutane sulfonate imide lithium (LiN).
  • LiPF 6 is preferable.
  • the lithium salt one kind may be used alone, or two or more kinds may be used in combination.
  • cellulose (SEC-K) into which a potassium ethylsulfonate group (or sodium ethylsulfonate group) was introduced was suction-filtered with a membrane filter made of polytetrafluoroethylene having a pore diameter of 0.1 ⁇ m, and the concentration was 70% by mass.
  • SEC-K cellulose
  • the washing was further washed with methanol, and the washed SEC-K was naturally dried for 24 hours.
  • SEC-K was vacuum dried at 105 ° C. for 10 hours.
  • the obtained SEC-K was dissolved in water to prepare an aqueous solution, and the aqueous solution was brought into contact with a strongly acidic ion exchange resin to obtain cellulose having a sulfoethyl group.
  • a 1M LiOH aqueous solution is added to the acidic aqueous solution of cellulose having a sulfoethyl group to neutralize it, the hydrogen atom of the sulfoethyl group is replaced with Li, and lithium ion conduction having the structure of the following formula as an example. LSP having sex was generated.
  • a dense cellulose film with no pores having a thickness of 17 ⁇ m was prepared, the obtained film was punched into a circle with a diameter of 12 cm, and the ionic conductivity was measured in the same manner as above. confirmed.
  • the alkali metal ion conductive solid electrolyte according to the present invention is suitable as a material for a non-aqueous electrolyte secondary battery.
  • Electrode group 2 Positive electrode lead 3: Negative electrode lead 4: Battery case 5: Seal plate, 6: Negative terminal terminal, 7: Gasket, 8: Seal

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PCT/JP2021/047655 2020-12-28 2021-12-22 アルカリ金属イオン伝導性固体電解質およびその製造方法、非水電解質二次電池用セパレータおよびその製造方法、ならびに非水電解質二次電池 Ceased WO2022145318A1 (ja)

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US18/269,392 US20240322232A1 (en) 2020-12-28 2021-12-22 Alkali metal ion-conductive solid electrolyte, method for producing same, separator for nonaqueous electrolyte secondary batteries, method for producing said separator for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
CN202180087749.2A CN116711089B (zh) 2020-12-28 2021-12-22 碱金属离子传导性固体电解质和其制造方法、非水电解质二次电池用分隔件和其制造方法、以及非水电解质二次电池

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